Organic electroluminescent materials and devices

ABSTRACT

Novel host compounds containing indolo[3,2,1-jk]carbazole moiety are disclosed. These compounds are useful in phosphorescent OLEDs and particularly as hosts and/or electron-blocking layer materials.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a non-provisional application claiming priorityunder 35 U.S.C. §119(e) to U.S. Provisional Application Ser. No.61/974,057, filed Apr. 2, 2014, the entire contents of which isincorporated herein by reference.

PARTIES TO A JOINT RESEARCH AGREEMENT

The claimed invention was made by, on behalf of, and/or in connectionwith one or more of the following parties to a joint universitycorporation research agreement: The Regents of the University ofMichigan, Princeton University, University of Southern California, andUniversal Display Corporation. The agreement was in effect on and beforethe date the claimed invention was made, and the claimed invention wasmade as a result of activities undertaken within the scope of theagreement.

FIELD OF THE INVENTION

The present invention relates to organic light emitting devices (OLEDs),and to organic materials used in such devices. More specifically, thepresent invention relates to novel organic materials for use as supportlayers in OLEDs, in particular as hosts and electron-blocking layermaterials, but not limited as such. The materials are based onindolo[3,2,1-jk]carbazole moiety. The compounds are expected to improvephosphorescent OLED performance.

BACKGROUND

Opto-electronic devices that make use of organic materials are becomingincreasingly desirable for a number of reasons. Many of the materialsused to make such devices are relatively inexpensive, so organicopto-electronic devices have the potential for cost advantages overinorganic devices. In addition, the inherent properties of organicmaterials, such as their flexibility, may make them well suited forparticular applications such as fabrication on a flexible substrate.Examples of organic opto-electronic devices include organic lightemitting devices (OLEDs), organic phototransistors, organic photovoltaiccells, and organic photodetectors. For OLEDs, the organic materials mayhave performance advantages over conventional materials. For example,the wavelength at which an organic emissive layer emits light maygenerally be readily tuned with appropriate dopants.

OLEDs make use of thin organic films that emit light when voltage isapplied across the device. OLEDs are becoming an increasinglyinteresting technology for use in applications such as flat paneldisplays, illumination, and backlighting. Several OLED materials andconfigurations are described in U.S. Pat. Nos. 5,844,363, 6,303,238, and5,707,745, which are incorporated herein by reference in their entirety.

One application for phosphorescent emissive molecules is a full colordisplay. Industry standards for such a display call for pixels adaptedto emit particular colors, referred to as “saturated” colors. Inparticular, these standards call for saturated red, green, and bluepixels. Color may be measured using CIE coordinates, which are wellknown to the art.

One example of a green emissive molecule is tris(2-phenylpyridine)iridium, denoted Ir(ppy)₃, which has the following structure:

In this, and later figures herein, we depict the dative bond fromnitrogen to metal (here, Ir) as a straight line.

As used herein, the term “organic” includes polymeric materials as wellas small molecule organic materials that may be used to fabricateorganic opto-electronic devices. “Small molecule” refers to any organicmaterial that is not a polymer, and “small molecules” may actually bequite large. Small molecules may include repeat units in somecircumstances. For example, using a long chain alkyl group as asubstituent does not remove a molecule from the “small molecule” class.Small molecules may also be incorporated into polymers, for example as apendent group on a polymer backbone or as a part of the backbone. Smallmolecules may also serve as the core moiety of a dendrimer, whichconsists of a series of chemical shells built on the core moiety. Thecore moiety of a dendrimer may be a fluorescent or phosphorescent smallmolecule emitter. A dendrimer may be a “small molecule,” and it isbelieved that all dendrimers currently used in the field of OLEDs aresmall molecules.

As used herein, “top” means furthest away from the substrate, while“bottom” means closest to the substrate. Where a first layer isdescribed as “disposed over” a second layer, the first layer is disposedfurther away from substrate. There may be other layers between the firstand second layer, unless it is specified that the first layer is “incontact with” the second layer. For example, a cathode may be describedas “disposed over” an anode, even though there are various organiclayers in between.

As used herein, “solution processible” means capable of being dissolved,dispersed, or transported in and/or deposited from a liquid medium,either in solution or suspension form.

A ligand may be referred to as “photoactive” when it is believed thatthe ligand directly contributes to the photoactive properties of anemissive material. A ligand may be referred to as “ancillary” when it isbelieved that the ligand does not contribute to the photoactiveproperties of an emissive material, although an ancillary ligand mayalter the properties of a photoactive ligand.

As used herein, and as would be generally understood by one skilled inthe art, a first “Highest Occupied Molecular Orbital” (HOMO) or “LowestUnoccupied Molecular Orbital” (LUMO) energy level is “greater than” or“higher than” a second HOMO or LUMO energy level if the first energylevel is closer to the vacuum energy level. Since ionization potentials(IP) are measured as a negative energy relative to a vacuum level, ahigher HOMO energy level corresponds to an IP having a smaller absolutevalue (an IP that is less negative). Similarly, a higher LUMO energylevel corresponds to an electron affinity (EA) having a smaller absolutevalue (an EA that is less negative). On a conventional energy leveldiagram, with the vacuum level at the top, the LUMO energy level of amaterial is higher than the HOMO energy level of the same material. A“higher” HOMO or LUMO energy level appears closer to the top of such adiagram than a “lower” HOMO or LUMO energy level.

As used herein, and as would be generally understood by one skilled inthe art, a first work function is “greater than” or “higher than” asecond work function if the first work function has a higher absolutevalue. Because work functions are generally measured as negative numbersrelative to vacuum level, this means that a “higher” work function ismore negative. On a conventional energy level diagram, with the vacuumlevel at the top, a “higher” work function is illustrated as furtheraway from the vacuum level in the downward direction. Thus, thedefinitions of HOMO and LUMO energy levels follow a different conventionthan work functions.

More details on OLEDs, and the definitions described above, can be foundin U.S. Pat. No. 7,279,704, which is incorporated herein by reference inits entirety.

SUMMARY OF THE INVENTION

According to an embodiment, a compound is provided that has thestructure according to a formula G¹-G²-G³-G⁴-G⁵, Formula I;

wherein G¹ has the structure:

-   -   wherein R¹ and R³ each independently represent mono, di, tri, or        tetra substitutions, or no substitution,    -   wherein R² represents mono, di, or tri substitutions, or no        substitution,    -   wherein R¹, R², and R³ are each independently selected from the        group consisting of hydrogen, deuterium, halogen, alkyl,        cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino,        silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl,        heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile,        isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and        combinations thereof;

wherein G² and G⁴ are each independently selected from the groupconsisting of a direct bond, an aryl group having from 6-30 carbonatoms, a heteroaryl group having from 3-30 carbon atoms, andcombinations thereof,

-   -   wherein the aryl group and the heteroaryl group are optionally        further substituted with one or more groups selected from        hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl,        arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl,        heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl,        carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl,        sulfonyl, phosphino, and combinations thereof; and

wherein G³ and G⁵ are each independently a carbazole or a carbazole thatis substituted with one or more groups selected from hydrogen,deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy,aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl,aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile,isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinationsthereof

According to another embodiment, a device comprising one or more organiclight emitting devices is also provided. At least one of the one or moreorganic light emitting devices can include an anode, a cathode, and anorganic layer, disposed between the anode and the cathode, wherein theorganic layer can include a compound of Formula I, including all of thevariations disclosed herein. The device can be a consumer product, anelectronic component module, an organic light-emitting device, and/or alighting panel.

According to yet another embodiment, a formulation containing thecompound of Formula I, including all of the variations, is alsoprovided.

Carbazole-containing compounds are known to be good hole-transporting,stable compounds in OLEDs, typically used in transport or host layers,but also as emitters. Use of the indolo[3,2,1-jk]carbazoles moiety inplace of carbazole can impart unique properties with respect tostability, charge transport and sublimation temperature. The presentdisclosure provides a series of indolo[3,2,1-jk]carbazole-containingmaterials that are superior support materials in OLED devices,particularly when used as host and/or electron-blocking layer (EBL)materials.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows an organic light emitting device.

FIG. 2 shows an inverted organic light emitting device that does nothave a separate electron transport layer.

DETAILED DESCRIPTION

Generally, an OLED comprises at least one organic layer disposed betweenand electrically connected to an anode and a cathode. When a current isapplied, the anode injects holes and the cathode injects electrons intothe organic layer(s). The injected holes and electrons each migratetoward the oppositely charged electrode. When an electron and holelocalize on the same molecule, an “exciton,” which is a localizedelectron-hole pair having an excited energy state, is formed. Light isemitted when the exciton relaxes via a photoemissive mechanism. In somecases, the exciton may be localized on an excimer or an exciplex.Non-radiative mechanisms, such as thermal relaxation, may also occur,but are generally considered undesirable.

The initial OLEDs used emissive molecules that emitted light from theirsinglet states (“fluorescence”) as disclosed, for example, in U.S. Pat.No. 4,769,292, which is incorporated by reference in its entirety.Fluorescent emission generally occurs in a time frame of less than 10nanoseconds.

More recently, OLEDs having emissive materials that emit light fromtriplet states (“phosphorescence”) have been demonstrated. Baldo et al.,“Highly Efficient Phosphorescent Emission from OrganicElectroluminescent Devices,” Nature, vol. 395, 151-154, 1998;(“Baldo-I”) and Baldo et al., “Very high-efficiency green organiclight-emitting devices based on electrophosphorescence,” Appl. Phys.Lett., vol. 75, No. 3, 4-6 (1999) (“Baldo-II”), which are incorporatedby reference in their entireties. Phosphorescence is described in moredetail in U.S. Pat. No. 7,279,704 at cols. 5-6, which are incorporatedby reference.

FIG. 1 shows an organic light emitting device 100. The figures are notnecessarily drawn to scale. Device 100 may include a substrate 110, ananode 115, a hole injection layer 120, a hole transport layer 125, anelectron blocking layer 130, an emissive layer 135, a hole blockinglayer 140, an electron transport layer 145, an electron injection layer150, a protective layer 155, a cathode 160, and a barrier layer 170.Cathode 160 is a compound cathode having a first conductive layer 162and a second conductive layer 164. Device 100 may be fabricated bydepositing the layers described, in order. The properties and functionsof these various layers, as well as example materials, are described inmore detail in U.S. Pat. No. 7,279,704 at cols. 6-10, which areincorporated by reference.

More examples for each of these layers are available. For example, aflexible and transparent substrate-anode combination is disclosed inU.S. Pat. No. 5,844,363, which is incorporated by reference in itsentirety. An example of a p-doped hole transport layer is m-MTDATA dopedwith F₄-TCNQ at a molar ratio of 50:1, as disclosed in U.S. PatentApplication Publication No. 2003/0230980, which is incorporated byreference in its entirety. Examples of emissive and host materials aredisclosed in U.S. Pat. No. 6,303,238 to Thompson et al., which isincorporated by reference in its entirety. An example of an n-dopedelectron transport layer is BPhen doped with Li at a molar ratio of 1:1,as disclosed in U.S. Patent Application Publication No. 2003/0230980,which is incorporated by reference in its entirety. U.S. Pat. Nos.5,703,436 and 5,707,745, which are incorporated by reference in theirentireties, disclose examples of cathodes including compound cathodeshaving a thin layer of metal such as Mg:Ag with an overlyingtransparent, electrically-conductive, sputter-deposited ITO layer. Thetheory and use of blocking layers is described in more detail in U.S.Pat. No. 6,097,147 and U.S. Patent Application Publication No.2003/0230980, which are incorporated by reference in their entireties.Examples of injection layers are provided in U.S. Patent ApplicationPublication No. 2004/0174116, which is incorporated by reference in itsentirety. A description of protective layers may be found in U.S. PatentApplication Publication No. 2004/0174116, which is incorporated byreference in its entirety.

FIG. 2 shows an inverted OLED 200. The device includes a substrate 210,a cathode 215, an emissive layer 220, a hole transport layer 225, and ananode 230. Device 200 may be fabricated by depositing the layersdescribed, in order. Because the most common OLED configuration has acathode disposed over the anode, and device 200 has cathode 215 disposedunder anode 230, device 200 may be referred to as an “inverted” OLED.Materials similar to those described with respect to device 100 may beused in the corresponding layers of device 200. FIG. 2 provides oneexample of how some layers may be omitted from the structure of device100.

The simple layered structure illustrated in FIGS. 1 and 2 is provided byway of non-limiting example, and it is understood that embodiments ofthe invention may be used in connection with a wide variety of otherstructures. The specific materials and structures described areexemplary in nature, and other materials and structures may be used.Functional OLEDs may be achieved by combining the various layersdescribed in different ways, or layers may be omitted entirely, based ondesign, performance, and cost factors. Other layers not specificallydescribed may also be included. Materials other than those specificallydescribed may be used. Although many of the examples provided hereindescribe various layers as comprising a single material, it isunderstood that combinations of materials, such as a mixture of host anddopant, or more generally a mixture, may be used. Also, the layers mayhave various sublayers. The names given to the various layers herein arenot intended to be strictly limiting. For example, in device 200, holetransport layer 225 transports holes and injects holes into emissivelayer 220, and may be described as a hole transport layer or a holeinjection layer. In one embodiment, an OLED may be described as havingan “organic layer” disposed between a cathode and an anode. This organiclayer may comprise a single layer, or may further comprise multiplelayers of different organic materials as described, for example, withrespect to FIGS. 1 and 2.

Structures and materials not specifically described may also be used,such as OLEDs comprised of polymeric materials (PLEDs) such as disclosedin U.S. Pat. No. 5,247,190 to Friend et al., which is incorporated byreference in its entirety. By way of further example, OLEDs having asingle organic layer may be used. OLEDs may be stacked, for example asdescribed in U.S. Pat. No. 5,707,745 to Forrest et al, which isincorporated by reference in its entirety. The OLED structure maydeviate from the simple layered structure illustrated in FIGS. 1 and 2.For example, the substrate may include an angled reflective surface toimprove out-coupling, such as a mesa structure as described in U.S. Pat.No. 6,091,195 to Forrest et al., and/or a pit structure as described inU.S. Pat. No. 5,834,893 to Bulovic et al., which are incorporated byreference in their entireties.

Unless otherwise specified, any of the layers of the various embodimentsmay be deposited by any suitable method. For the organic layers,preferred methods include thermal evaporation, ink-jet, such asdescribed in U.S. Pat. Nos. 6,013,982 and 6,087,196, which areincorporated by reference in their entireties, organic vapor phasedeposition (OVPD), such as described in U.S. Pat. No. 6,337,102 toForrest et al., which is incorporated by reference in its entirety, anddeposition by organic vapor jet printing (OVJP), such as described inU.S. Pat. No. 7,431,968, which is incorporated by reference in itsentirety. Other suitable deposition methods include spin coating andother solution based processes. Solution based processes are preferablycarried out in nitrogen or an inert atmosphere. For the other layers,preferred methods include thermal evaporation. Preferred patterningmethods include deposition through a mask, cold welding such asdescribed in U.S. Pat. Nos. 6,294,398 and 6,468,819, which areincorporated by reference in their entireties, and patterning associatedwith some of the deposition methods such as ink jet and OVJD. Othermethods may also be used. The materials to be deposited may be modifiedto make them compatible with a particular deposition method. Forexample, substituents such as alkyl and aryl groups, branched orunbranched, and preferably containing at least 3 carbons, may be used insmall molecules to enhance their ability to undergo solution processing.Substituents having 20 carbons or more may be used, and 3-20 carbons isa preferred range. Materials with asymmetric structures may have bettersolution processibility than those having symmetric structures, becauseasymmetric materials may have a lower tendency to recrystallize.Dendrimer substituents may be used to enhance the ability of smallmolecules to undergo solution processing.

Devices fabricated in accordance with embodiments of the presentinvention may further optionally comprise a barrier layer. One purposeof the barrier layer is to protect the electrodes and organic layersfrom damaging exposure to harmful species in the environment includingmoisture, vapor and/or gases, etc. The barrier layer may be depositedover, under or next to a substrate, an electrode, or over any otherparts of a device including an edge. The barrier layer may comprise asingle layer, or multiple layers. The barrier layer may be formed byvarious known chemical vapor deposition techniques and may includecompositions having a single phase as well as compositions havingmultiple phases. Any suitable material or combination of materials maybe used for the barrier layer. The barrier layer may incorporate aninorganic or an organic compound or both. The preferred barrier layercomprises a mixture of a polymeric material and a non-polymeric materialas described in U.S. Pat. No. 7,968,146, PCT Pat. Application Nos.PCT/US2007/023098 and PCT/US2009/042829, which are herein incorporatedby reference in their entireties. To be considered a “mixture”, theaforesaid polymeric and non-polymeric materials comprising the barrierlayer should be deposited under the same reaction conditions and/or atthe same time. The weight ratio of polymeric to non-polymeric materialmay be in the range of 95:5 to 5:95. The polymeric material and thenon-polymeric material may be created from the same precursor material.In one example, the mixture of a polymeric material and a non-polymericmaterial consists essentially of polymeric silicon and inorganicsilicon.

Devices fabricated in accordance with embodiments of the invention canbe incorporated into a wide variety of electronic component modules (orunits) that can be incorporated into a variety of electronic products orintermediate components. Examples of such electronic products orintermediate components include display screens, lighting devices suchas discrete light source devices or lighting panels, etc. that can beutilized by the end-user product manufacturers. Such electroniccomponent modules can optionally include the driving electronics and/orpower source(s). Devices fabricated in accordance with embodiments ofthe invention can be incorporated into a wide variety of consumerproducts that have one or more of the electronic component modules (orunits) incorporated therein. Such consumer products would include anykind of products that include one or more light source(s) and/or one ormore of some type of visual displays. Some examples of such consumerproducts include flat panel displays, computer monitors, medicalmonitors, televisions, billboards, lights for interior or exteriorillumination and/or signaling, heads-up displays, fully or partiallytransparent displays, flexible displays, laser printers, telephones,cell phones, tablets, phablets, personal digital assistants (PDAs),laptop computers, digital cameras, camcorders, viewfinders,micro-displays, 3-D displays, vehicles, a large area wall, theater orstadium screen, or a sign. Various control mechanisms may be used tocontrol devices fabricated in accordance with the present invention,including passive matrix and active matrix. Many of the devices areintended for use in a temperature range comfortable to humans, such as18 degrees C. to 30 degrees C., and more preferably at room temperature(20-25 degrees C.), but could be used outside this temperature range,for example, from −40 degree C. to +80 degree C.

The materials and structures described herein may have applications indevices other than OLEDs. For example, other optoelectronic devices suchas organic solar cells and organic photodetectors may employ thematerials and structures. More generally, organic devices, such asorganic transistors, may employ the materials and structures.

The term “halo,” “halogen,” or “halide” as used herein includesfluorine, chlorine, bromine, and iodine.

The term “alkyl” as used herein contemplates both straight and branchedchain alkyl radicals. Preferred alkyl groups are those containing fromone to fifteen carbon atoms and includes methyl, ethyl, propyl,isopropyl, butyl, isobutyl, tert-butyl, and the like. Additionally, thealkyl group may be optionally substituted.

The term “cycloalkyl” as used herein contemplates cyclic alkyl radicals.Preferred cycloalkyl groups are those containing 3 to 7 carbon atoms andincludes cyclopropyl, cyclopentyl, cyclohexyl, and the like.Additionally, the cycloalkyl group may be optionally substituted.

The term “alkenyl” as used herein contemplates both straight andbranched chain alkene radicals. Preferred alkenyl groups are thosecontaining two to fifteen carbon atoms. Additionally, the alkenyl groupmay be optionally substituted.

The term “alkynyl” as used herein contemplates both straight andbranched chain alkyne radicals. Preferred alkyl groups are thosecontaining two to fifteen carbon atoms. Additionally, the alkynyl groupmay be optionally substituted.

The terms “aralkyl” or “arylalkyl” as used herein are usedinterchangeably and contemplate an alkyl group that has as a substituentan aromatic group. Additionally, the aralkyl group may be optionallysubstituted.

The term “heterocyclic group” as used herein contemplates aromatic andnon-aromatic cyclic radicals. Hetero-aromatic cyclic radicals also meansheteroaryl. Preferred hetero-non-aromatic cyclic groups are thosecontaining 3 or 7 ring atoms which includes at least one hetero atom,and includes cyclic amines such as morpholino, piperdino, pyrrolidino,and the like, and cyclic ethers, such as tetrahydrofuran,tetrahydropyran, and the like. Additionally, the heterocyclic group maybe optionally substituted.

The term “aryl” or “aromatic group” as used herein contemplatessingle-ring groups and polycyclic ring systems. The polycyclic rings mayhave two or more rings in which two carbons are common to two adjoiningrings (the rings are “fused”) wherein at least one of the rings isaromatic, e.g., the other rings can be cycloalkyls, cycloalkenyls, aryl,heterocycles, and/or heteroaryls. Additionally, the aryl group may beoptionally substituted.

The term “heteroaryl” as used herein contemplates single-ringhetero-aromatic groups that may include from one to three heteroatoms,for example, pyrrole, furan, thiophene, imidazole, oxazole, thiazole,triazole, pyrazole, pyridine, pyrazine and pyrimidine, and the like. Theterm heteroaryl also includes polycyclic hetero-aromatic systems havingtwo or more rings in which two atoms are common to two adjoining rings(the rings are “fused”) wherein at least one of the rings is aheteroaryl, e.g., the other rings can be cycloalkyls, cycloalkenyls,aryl, heterocycles, and/or heteroaryls. Additionally, the heteroarylgroup may be optionally substituted.

The alkyl, cycloalkyl, alkenyl, alkynyl, aralkyl, heterocyclic group,aryl, and heteroaryl may be optionally substituted with one or moresubstituents selected from the group consisting of hydrogen, deuterium,halogen, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy,amino, cyclic amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl,alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ether,ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, andcombinations thereof

As used herein, “substituted” indicates that a substituent other than His bonded to the relevant position, such as carbon. Thus, for example,where R¹ is mono-substituted, then one R¹ must be other than H.Similarly, where R¹ is di-substituted, then two of R¹ must be other thanH. Similarly, where R¹ is unsubstituted, R¹ is hydrogen for allavailable positions.

The “aza” designation in the fragments described herein, i.e.aza-dibenzofuran, aza-dibenzonethiophene, etc. means that one or more ofthe C—H groups in the respective fragment can be replaced by a nitrogenatom, for example, and without any limitation, azatriphenyleneencompasses both dibenzo[f,h]quinoxaline and dibenzo[f,h]quinoline. Oneof ordinary skill in the art can readily envision other nitrogen analogsof the aza-derivatives described above, and all such analogs areintended to be encompassed by the terms as set forth herein.

It is to be understood that when a molecular fragment is described asbeing a substituent or otherwise attached to another moiety, its namemay be written as if it were a fragment (e.g. phenyl, phenylene,naphthyl, dibenzofuryl) or as if it were the whole molecule (e.g.benzene, naphthalene, dibenzofuran). As used herein, these differentways of designating a substituent or attached fragment are considered tobe equivalent.

According to an aspect of the present disclosure, a compound having aformula G¹-G²-G³-G⁴-G⁵, Formula I, disclosed. In Formula I, G¹ has thestructure:

-   -   wherein R¹ and R³ each independently represent mono, di, tri, or        tetra substitutions, or no substitution,    -   wherein R² represents mono, di, or tri substitutions, or no        substitution,    -   wherein R¹, R², and R³ are each independently selected from the        group consisting of hydrogen, deuterium, halogen, alkyl,        cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino,        silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl,        heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile,        isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and        combinations thereof;

wherein G² and G⁴ are each independently selected from the groupconsisting of a direct bond, an aryl group having from 6-30 carbonatoms, a heteroaryl group having from 3-30 carbon atoms, andcombinations thereof,

-   -   wherein the aryl group and the heteroaryl group are optionally        further substituted with one or more groups selected from        hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl,        arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl,        heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl,        carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl,        sulfonyl, phosphino, and combinations thereof and

wherein G³ and G⁵ are each independently a carbazole or a carbazole thatis substituted with one or more groups selected from hydrogen,deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy,aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl,aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile,isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinationsthereof

In one embodiment of the compound, G¹ connects to G² at the ring havingR² substituent.

In another embodiment, G¹ connects to G² at the ring having R³substituent.

In one embodiment, G² and G⁴ are each a direct bond.

In one embodiment, the compound of Formula I has a structure:

-   -   wherein R⁴ represents mono, di, tri, or tetra substitutions, or        no substitution;    -   wherein R⁵ represents mono, di, or tri substitutions, or no        substitution;    -   wherein R⁴ and R⁵ are each independently selected from the group        consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl,        heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl,        cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl,        carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl,        sulfinyl, sulfonyl, phosphino, and combinations thereof

In another embodiment, the compound of Formula I has a structure:

-   -   wherein R⁶, and R⁷ each independently represents mono, di, tri,        or tetra substitutions, or no substitution;    -   wherein R⁶, and R⁷ are each independently selected from the        group consisting of hydrogen, deuterium, halogen, alkyl,        cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino,        silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl,        heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile,        isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and        combinations thereof

In another embodiment, the compound of Formula I has a structureselected from the group consisting of:

wherein R⁴ represents mono, di, or tri substitutions, or nosubstitution;

wherein R⁵ represents mono, di, tri, or tetra substitutions, or nosubstitution;

wherein R⁴, R⁵, and R⁸ are each independently selected from the groupconsisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl,heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl,cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl,carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl,sulfonyl, phosphino, and combinations thereof

In another embodiment, the compound of Formula I has a structure:

wherein R⁶, and R⁷ each independently represents mono, di, tri, or tetrasubstitutions, or no substitution;

wherein R⁶, R⁷, and R⁹ are each independently selected from the groupconsisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl,heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl,cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl,carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl,sulfonyl, phosphino, and combinations thereof

In some embodiments, the compound of Formula I has a structure selectedfrom the group consisting of:

wherein R⁴, R⁶, and R⁷ each independently represents mono, di, tri, ortetra substitutions, or no substitution;

wherein R⁵ represents mono, di, or tri, substitutions, or nosubstitution;

wherein R⁴, R⁵, R⁶, R⁷, R⁸, and R⁹ are each independently selected fromthe group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl,heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl,cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl,carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl,sulfonyl, phosphino, and combinations thereof

In another embodiment of the compound of Formula I, G¹ is selected fromthe group consisting of:

In another embodiment of the compound of Formula I, the compound isselected from the group consisting of:

According to another aspect of the present disclosure, a devicecomprising one or more organic light emitting devices is disclosed. Atleast one of the one or more organic light emitting devices comprise: ananode; a cathode; and an organic layer, disposed between the anode andthe cathode. In one embodiment, the organic layer comprises a compoundhaving the formula G¹-G²-G³-G⁴-G⁵, Formula I;

wherein G¹ has the structure:

-   -   wherein R¹ and R³ each independently represent mono, di, tri, or        tetra substitution, or no substitution;    -   wherein R² represents mono, di, or tri substitution, or no        substitution;    -   wherein R¹, R², and R³ are each independently selected from the        group consisting of hydrogen, deuterium, halogen, alkyl,        cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino,        silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl,        heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile,        isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and        combinations thereof;

wherein G² and G⁴ are each independently selected from the groupconsisting of a direct bond, an aryl group having from 6-30 carbonatoms, a heteroaryl group having from 3-30 carbon atoms, andcombinations thereof; wherein the aryl group and the heteroaryl groupare optionally further substituted with one or more groups selected fromhydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, arylalkyl,alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl,alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester,nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, andcombinations thereof; and

wherein G³ and G⁵ are each independently a carbazole or a carbazole thatis substituted with one or more groups selected from hydrogen,deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy,aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl,aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile,isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinationsthereof

In one embodiment of the device, the organic layer is an emissive layerand the compound is a host.

In another embodiment, the organic layer further comprises aphosphorescent emissive dopant. The phosphorescent emissive dopant canbe a transition metal complex having at least one ligand or part of theligand, if the ligand is more than bidentate, selected from the groupconsisting of:

-   -   wherein R_(a), R_(b), R_(c), and R_(d) may represent mono, di,        tri, or tetra substitution, or no substitution;

wherein R_(a), R_(b), R_(c), and R_(d) are independently selected fromthe group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl,heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl,cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl,carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl,sulfonyl, phosphino, and combinations thereof; and

wherein two adjacent substituents of R_(a), R_(b), R_(c), and R_(d) areoptionally joined to form a fused ring or form a multidentate ligand.

In another embodiment of the device, the phosphorescent emissive dopantcan be selected from the group consisting of:

In another embodiment of the device, the organic layer is an electronblocking layer and the compound having Formula I is an electron blockingmaterial in the organic layer.

In another embodiment of the device, the organic layer is an electrontransporting layer and the compound having Formula I is an electrontransporting material in the organic layer.

In another embodiment, the device is selected from the group consistingof a consumer product, an electronic component module, an organiclight-emitting device, and a lighting panel.

In yet another aspect of the present disclosure, a formulation thatcomprises a compound according to Formula I, and its variations asdescribed herein, is described. The formulation can include one or morecomponents selected from the group consisting of a solvent, a host, ahole injection material, hole transport material, and an electrontransport layer material, disclosed herein.

Combination with Other Materials

The materials described herein as useful for a particular layer in anorganic light emitting device may be used in combination with a widevariety of other materials present in the device. For example, emissivedopants disclosed herein may be used in conjunction with a wide varietyof hosts, transport layers, blocking layers, injection layers,electrodes and other layers that may be present. The materials describedor referred to below are non-limiting examples of materials that may beuseful in combination with the compounds disclosed herein, and one ofskill in the art can readily consult the literature to identify othermaterials that may be useful in combination.

HIL/HTL:

A hole injecting/transporting material to be used in the presentinvention is not particularly limited, and any compound may be used aslong as the compound is typically used as a hole injecting/transportingmaterial. Examples of the material include, but are not limited to: aphthalocyanine or porphyrin derivative; an aromatic amine derivative; anindolocarbazole derivative; a polymer containing fluorohydrocarbon; apolymer with conductivity dopants; a conducting polymer, such asPEDOT/PSS; a self-assembly monomer derived from compounds such asphosphonic acid and silane derivatives; a metal oxide derivative, suchas MoO_(x); a p-type semiconducting organic compound, such as1,4,5,8,9,12-Hexaazatriphenylenehexacarbonitrile; a metal complex, and across-linkable compound.

Examples of aromatic amine derivatives used in HIL or HTL include, butare not limited to the following general structures:

Each of Ar¹ to Ar⁹ is selected from the group consisting aromatichydrocarbon cyclic compounds such as benzene, biphenyl, triphenyl,triphenylene, naphthalene, anthracene, phenalene, phenanthrene,fluorene, pyrene, chrysene, perylene, azulene; group consisting aromaticheterocyclic compounds such as dibenzothiophene, dibenzofuran,dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene,benzoselenophene, carbazole, indolocarbazole, pyridylindole,pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole,oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine,pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine,indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole,benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline,quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine,phenazine, phenothiazine, phenoxazine, benzofuropyridine,furodipyridine, benzothienopyridine, thienodipyridine,benzoselenophenopyridine, and selenophenodipyridine; and groupconsisting 2 to 10 cyclic structural units which are groups of the sametype or different types selected from the aromatic hydrocarbon cyclicgroup and the aromatic heterocyclic group and are bonded to each otherdirectly or via at least one of oxygen atom, nitrogen atom, sulfur atom,silicon atom, phosphorus atom, boron atom, chain structural unit and thealiphatic cyclic group. Wherein each Ar is further substituted by asubstituent selected from the group consisting of hydrogen, deuterium,halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy,amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl,heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile,isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinationsthereof

In one aspect, Ar¹ to Ar⁹ is independently selected from the groupconsisting of:

wherein k is an integer from 1 to 20; X¹⁰¹ to X¹⁰⁸ is C (including CH)or N; Z¹⁰¹ is NAr¹, O, or S; Ar¹ has the same group defined above.

Examples of metal complexes used in HIL or HTL include, but not arelimited to the following general formula:

wherein Met is a metal, which can have an atomic weight greater than 40;(Y¹⁰¹-Y¹⁰²) is a bidentate ligand, Y¹⁰¹ and Y¹⁰² are independentlyselected from C, N, O, P, and S; L¹⁰¹ is an ancillary ligand; k′ is aninteger value from 1 to the maximum number of ligands that may beattached to the metal; and k′+k″ is the maximum number of ligands thatmay be attached to the metal.

In one aspect, (Y¹⁰¹-Y¹⁰²) is a 2-phenylpyridine derivative. In anotheraspect, (Y¹⁰¹-Y¹⁰²) is a carbene ligand. In another aspect, Met isselected from Ir, Pt, Os, and Zn. In a further aspect, the metal complexhas a smallest oxidation potential in solution vs. Fc⁺/Fc couple lessthan about 0.6 V.

Host:

The light emitting layer of the organic EL device of the presentinvention preferably contains at least a metal complex as light emittingmaterial, and may contain a host material using the metal complex as adopant material. Examples of the host material are not particularlylimited, and any metal complexes or organic compounds may be used aslong as the triplet energy of the host is larger than that of thedopant. While the Table below categorizes host materials as preferredfor devices that emit various colors, any host material may be used withany dopant so long as the triplet criteria is satisfied.

Examples of metal complexes used as host are preferred to have thefollowing general formula:

wherein Met is a metal; (Y¹⁰³-Y¹⁰⁴) is a bidentate ligand, Y¹⁰³ and Y¹⁰⁴are independently selected from C, N, O, P, and S; L¹⁰¹ is an anotherligand; k′ is an integer value from 1 to the maximum number of ligandsthat may be attached to the metal; and k′+k″ is the maximum number ofligands that may be attached to the metal.

In one aspect, the metal complexes are:

wherein (O—N) is a bidentate ligand, having metal coordinated to atoms Oand N.

In another aspect, Met is selected from Ir and Pt. In a further aspect,(Y¹⁰³-Y¹⁰⁴) is a carbene ligand.

Examples of organic compounds used as host are selected from the groupconsisting aromatic hydrocarbon cyclic compounds such as benzene,biphenyl, triphenyl, triphenylene, naphthalene, anthracene, phenalene,phenanthrene, fluorene, pyrene, chrysene, perylene, azulene; groupconsisting aromatic heterocyclic compounds such as dibenzothiophene,dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran,benzothiophene, benzoselenophene, carbazole, indolocarbazole,pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole,oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole,pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine,oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine,benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline,cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine,pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine,benzofuropyridine, furodipyridine, benzothienopyridine,thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine;and group consisting 2 to 10 cyclic structural units which are groups ofthe same type or different types selected from the aromatic hydrocarboncyclic group and the aromatic heterocyclic group and are bonded to eachother directly or via at least one of oxygen atom, nitrogen atom, sulfuratom, silicon atom, phosphorus atom, boron atom, chain structural unitand the aliphatic cyclic group. Wherein each group is furthersubstituted by a substituent selected from the group consisting ofhydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl,alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl,alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester,nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, andcombinations thereof

In one aspect, host compound contains at least one of the followinggroups in the molecule:

wherein R¹⁰¹ to R¹⁰⁷ is independently selected from the group consistingof hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl,arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl,heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylicacids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl,phosphino, and combinations thereof, when it is aryl or heteroaryl, ithas the similar definition as Ar's mentioned above. k is an integer from0 to 20 or 1 to 20; k′ is an integer from 0 to 20. X¹⁰¹ to X¹⁰⁸ isselected from C (including CH) or N. Z¹⁰¹ and Z¹⁰² is selected fromNR¹⁰¹, O, or S.

HBL:

A hole blocking layer (HBL) may be used to reduce the number of holesand/or excitons that leave the emissive layer. The presence of such ablocking layer in a device may result in substantially higherefficiencies as compared to a similar device lacking a blocking layer.Also, a blocking layer may be used to confine emission to a desiredregion of an OLED.

In one aspect, compound used in HBL contains the same molecule or thesame functional groups used as host described above.

In another aspect, compound used in HBL contains at least one of thefollowing groups in the molecule:

wherein k is an integer from 1 to 20; L¹⁰¹ is an another ligand, k′ isan integer from 1 to 3.

ETL:

Electron transport layer (ETL) may include a material capable oftransporting electrons. Electron transport layer may be intrinsic(undoped), or doped. Doping may be used to enhance conductivity.Examples of the ETL material are not particularly limited, and any metalcomplexes or organic compounds may be used as long as they are typicallyused to transport electrons.

In one aspect, compound used in ETL contains at least one of thefollowing groups in the molecule:

wherein R¹⁰¹ is selected from the group consisting of hydrogen,deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy,aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl,aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile,isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinationsthereof, when it is aryl or heteroaryl, it has the similar definition asAr's mentioned above. Ar¹ to Ar³ has the similar definition as Ar'smentioned above. k is an integer from 1 to 20. X¹⁰¹ to X¹⁰⁸ is selectedfrom C (including CH) or N.

In another aspect, the metal complexes used in ETL include, but are notlimited to the following general formula:

wherein (O—N) or (N—N) is a bidentate ligand, having metal coordinatedto atoms O, N or N, N; L¹⁰¹ is another ligand; k′ is an integer valuefrom 1 to the maximum number of ligands that may be attached to themetal.

In any above-mentioned compounds used in each layer of the OLED device,the hydrogen atoms can be partially or fully deuterated. Thus, anyspecifically listed substituent, such as, without limitation, methyl,phenyl, pyridyl, etc. encompasses undeuterated, partially deuterated,and fully deuterated versions thereof. Similarly, classes ofsubstituents such as, without limitation, alkyl, aryl, cycloalkyl,heteroaryl, etc. also encompass undeuterated, partially deuterated, andfully deuterated versions thereof.

In addition to and/or in combination with the materials disclosedherein, many hole injection materials, hole transporting materials, hostmaterials, dopant materials, exciton/hole blocking layer materials,electron transporting and electron injecting materials may be used in anOLED. Non-limiting examples of the materials that may be used in an OLEDin combination with materials disclosed herein are listed in Table Abelow. Table A lists non-limiting classes of materials, non-limitingexamples of compounds for each class, and references that disclose thematerials.

TABLE A MATERIAL EXAMPLES OF MATERIAL PUBLICATIONS Hole injectionmaterials Phthalocyanine and porphryin compounds

Appl. Phys. Lett. 69, 2160 (1996) Starburst triarylamines

J. Lumin. 72-74, 985 (1997) CF_(x) Fluorohydrocarbon CH_(x)F_(y)_(n)Appl. Phys. Lett. polymer 78, 673 (2001) Conducting polymers (e.g.,PEDOT:PSS, polyaniline, polythiophene)

Synth. Met. 87, 171 (1997) WO2007002683 Phosphonic acid and silane SAMs

US20030162053 Triarylamine or polythiophene polymers with conductivitydopants

  and  

 

EP1725079A1 Organic compounds with conductive inorganic compounds, suchas molybdenum and tungsten oxides

US20050123751 SID Symposium Digest, 37, 923 (2006) WO2009018009 n-typesemiconducting organic complexes

US20020158242 Metal organometallic complexes

US20060240279 Cross-linkable compounds

US20080220265 Polythiophene based polymers and copolymers

WO 2011075644 EP2350216 Hole transporting materials Triarylamines (e.g.,TPD, α-NPD)

Appl. Phys. Lett. 51, 913 (1987)

U.S. Pat. No. 5,061,569

EP650955

J. Mater. Chem. 3, 319 (1993)

Appl. Phys. Lett. 90, 183503 (2007)

Appl. Phys. Lett. 90, 183503 (2007) Triarylamine on spirofluorene core

Synth. Met. 91, 209 (1997) Arylamine carbazole compounds

Adv. Mater. 6, 677 (1994), US20080124572 Triarylamine with(di)benzothiophene/ (di)benzofuran

US20070278938, US20080106190 US20110163302 Indolocarbazoles

Synth. Met. 111, 421 (2000) Isoindole compounds

Chem. Mater. 15, 3148 (2003) Metal carbene complexes

US20080018221 Phosphorescent OLED host materials Red hostsArylcarbazoles

Appl. Phys. Lett. 78, 1622 (2001) Metal 8- hydroxyquinolates (e.g.,Alq₃, BAlq)

Nature 395, 151 (1998)

US20060202194

WO2005014551

WO2006072002 Metal phenoxybenzothiazole compounds

Appl. Phys. Lett. 90, 123509 (2007) Conjugated oligomers and polymers(e.g., polyfluorene)

Org. Electron. 1, 15 (2000) Aromatic fused rings

WO2009066779, WO2009066778, WO2009063833, US20090045731, US20090045730,WO2009008311, US20090008605, US20090009065 Zinc complexes

WO2010056066 Chrysene based compounds

WO2011086863 Green hosts Arylcarbazoles

Appl. Phys. Lett. 78, 1622 (2001)

US20030175553

WO2001039234 Aryltriphenylene compounds

US20060280965

US20060280965

WO2009021126 Poly-fused heteroaryl compounds

US20090309488 US20090302743 US20100012931 Donor acceptor type molecules

WO2008056746

WO2010107244 Aza- carbazole/DBT/DBF

JP2008074939

US20100187984 Polymers (e.g., PVK)

Appl. Phys. Lett. 77, 2280 (2000) Spirofluorene compounds

WO2004093207 Metal phenoxybenzooxazole compounds

WO2005089025

WO2006132173

JP200511610 Spirofluorene-carbazole compounds

JP2007254297

JP2007254297 Indolocarbazoles

WO2007063796

WO2007063754 5-member ring electron deficient heterocycles (e.g.,triazole, oxadiazole)

J. Appl. Phys. 90, 5048 (2001)

WO2004107822 Tetraphenylene complexes

US20050112407 Metal phenoxypyridine compounds

WO2005030900 Metal coordination complexes (e.g., Zn, Al withN{circumflex over ( )}N ligands)

US20040137268, US20040137267 Blue Hosts Arylcarbazoles

Appl. Phys. Lett, 82, 2422 (2003)

US20070190359 Dibenzo- thiophene/Dibenzo- furan-carbazole compounds

WO2006114966, US20090167162

US20090167162

WO2009086028

US20090030202, US20090017330

US20100084966 Silicon aryl compounds

US20050238919

WO2009003898 Silicon/Germanium aryl compounds

EP2034538A Aryl benzoyl ester

WO2006100298 Carbazole linked by non-conjugated groups

US20040115476 Aza-carbazoles

US20060121308 High triplet metal organometallic complex

U.S. Pat. No. 7,154,114 Phosphorescent dopants Red dopants Heavy metalporphyrins (e.g., PtOEP)

Nature 395, 151 (1998) Iridium(III) organometallic complexes

Appl. Phys. Lett. 78, 1622 (2001)

US20030072964

US20030072964

US20060202194

US20060202194

US20070087321

US20080261076 US20100090591

US20070087321

Adv. Mater. 19, 739 (2007)

WO2009100991

WO2008101842

U.S. Pat. No. 7,232,618 Platinum(II) organometallic complexes

WO2003040257

US20070103060 Osminum(III) complexes

Chem. Mater. 17, 3532 (2005) Ruthenium(II) complexes

Adv. Mater. 17, 1059 (2005) Rhenium (I), (II), and (III) complexes

US20050244673 Green dopants Iridium(III) organometallic complexes

  and its derivatives Inorg. Chem. 40, 1704 (2001)

US20020034656

U.S. Pat. No. 7,332,232

US20090108737

WO2010028151

EP1841834B

US20060127696

US20090039776

U.S. Pat. No. 6,921,915

US20100244004

U.S. Pat. No. 6,687,266

Chem. Mater. 16, 2480 (2004)

US20070190359

US 20060008670 JP2007123392

WO2010086089, WO2011044988

Adv. Mater. 16, 2003 (2004)

Angew. Chem. Int. Ed. 2006, 45, 7800

WO2009050290

US20090165846

US20080015355

US20010015432

US20100295032 Monomer for polymeric metal organometallic compounds

U.S. Pat. No. 7,250,226, U.S. Pat. No. 7,396,598 Pt(II) organometalliccomplexes, including polydentate ligands

Appl. Phys. Lett. 86, 153505 (2005)

Appl. Phys. Lett. 86, 153505 (2005)

Chem. Lett. 34, 592 (2005)

WO2002015645

US20060263635

US20060182992 US20070103060 Cu complexes

WO2009000673

US20070111026 Gold complexes

Chem. Commun. 2906 (2005) Rhenium(III) complexes

Inorg. Chem. 42, 1248 (2003) Osmium(II) complexes

U.S. Pat. No. 7,279,704 Deuterated organometallic complexes

US20030138657 Organometallic complexes with two or more metal centers

US20030152802

U.S. Pat. No. 7,090,928 Blue dopants Iridium(III) organometalliccomplexes

WO2002002714

WO2006009024

US20060251923 US20110057559 US20110204333

U.S. Pat. No. 7,393,599, WO2006056418, US20050260441, WO2005019373

U.S. Pat. No. 7,534,505

WO2011051404

U.S. Pat. No. 7,445,855

US20070190359, US20080297033 US20100148663

U.S. Pat. No. 7,338,722

US20020134984

Angew. Chem. Int. Ed. 47, 4542 (2008)

Chem. Mater. 18, 5119 (2006)

Inorg. Chem. 46, 4308 (2007)

WO2005123873

WO2005123873

WO2007004380

WO2006082742 Osmium(II) complexes

U.S. Pat. No. 7,279,704

Organometallics 23, 3745 (2004) Gold complexes

Appl. Phys. Lett. 74, 1361 (1999) Platinum(II) complexes

WO2006098120, WO2006103874 Pt tetradentate complexes with at least onemetal- carbene bond

U.S. Pat. No. 7,655,323 Exicton/hole blocking layer materialsBathocuprine compounds (e.g., BCP, BPhen)

Appl. Phys. Lett. 75, 4 (1999)

Appl. Phys. Lett. 79, 449 (2001) Metal 8-hydroxyquinolates (e.g., BAlq)

Appl. Phys. Lett. 81, 162 (2002) 5-member ring electron deficientheterocycles such as triazole, oxadiazole, imidazole, benzoimidazole

Appl. Phys. Lett. 81, 162 (2002) Triphenylene compounds

US20050025993 Fluorinated aromatic compounds

Appl. Phys. Lett. 79, 156 (2001) Phenothiazine-S-oxide

WO2008132085 Silylated five-membered nitrogen, oxygen, sulfur orphosphorus dibenzoheterocycles

WO2010079051 Aza-carbazoles

US20060121308 Electron transporting materials Anthracene- benzoimidazolecompounds

WO2003060956

US20090179554 Aza triphenylene derivatives

US20090115316 Anthracene-benzothiazole compounds

Appl. Phys. Lett. 89, 063504 (2006) Metal 8-hydroxyquinolates (e.g.,Alq₃, Zrq₄)

Appl. Phys. Lett. 51, 913 (1987) U.S. Pat. No. 7,230,107 Metalhydroxybenoquinolates

Chem. Lett. 5, 905 (1993) Bathocuprine compounds such as BCP, BPhen, etc

Appl. Phys. Lett. 91, 263503 (2007)

Appl. Phys. Lett. 79, 449 (2001) 5-member ring electron deficientheterocycles (e.g., triazole, oxadiazole, imidazole, benzoimidazole)

Appl. Phys. Lett. 74, 865 (1999)

Appl. Phys. Lett. 55, 1489 (1989)

Jpn. J. Apply. Phys. 32, L917 (1993) Silole compounds

Org. Electron. 4, 113 (2003) Arylborane compounds

J. Am. Chem. Soc. 120, 9714 (1998) Fluorinated aromatic compounds

J. Am. Chem. Soc. 122, 1832 (2000) Fullerene (e.g., C₆₀)

US20090101870 Triazine complexes

US20040036077 Zn (N{circumflex over ( )}N) complexes

U.S. Pat. No. 6,528,187

SYNTHESIS OF COMPOUNDS

Synthesis of9-(2-bromophenyl)-9H-carbazole/9-(2-iodophenyl)-9H-carbazole Mixture

9H-carbazole (9.8 g, 58.9 mmol) and 1-bromo-2-iodobenzene (50 g, 177mmol) were mixed with copper (0.94 g, 14.7 mmol) and potassium carbonate(16.3 g, 118 mmol) and the slurry was heated to 200° C. for 12 hours.After cooling to room temperature, the reaction was filtered throughcelite, washing with DCM. The DCM was removed under reduced pressure andthe excess 1-bromo-2-iodobenzene was removed by Kugelrohr distillation.The residue was then chromatographed on silica with 0-3% DCM in hetaneand recrystallized from heptane to yield 14.4 g of a mixture of9-(2-bromophenyl)-9H-carbazole (˜60%) and 9-(2-iodophenyl)-9H-carbazole(˜40%).

Synthesis of 9-(2-bromo-5-chlorophenyl)-9H-carbazole

2-bromo-5-chloroaniline (7.9 g, 38.4 mmol), 2,2′-diiodo-1,1′-biphenyl(13.0 g, 32.0 mmol), Pd₂(dba)₃ (0.59 g, 0.64 mmol) andtricyclohexylphosphine (0.72 g, 2.6 mmol) were added to toluene (250 mL)followed by sodium tert-butoxide (9.2 g, 96 mmol). The mixture wasdegassed thoroughly before being heated to reflux for 4 hours. The crudereaction mixture was cooled and filtered through a celite plug, washingwith toluene and DCM. The filtrate was rotovapped to give 14.7 g of adark oil, which was chromatographed on silica gel with 99/1 heptane/DCMto 90/10 heptane DCM to give 9.5 g (83%) of9-(2-bromo-5-chlorophenyl)-9H-carbazole, which was used without furtherpurification.

Synthesis of indolo[3,2,1-jk]carbazole

A mixture of 9-(2-bromophenyl)-9H-carbazole (˜60%) and9-(2-iodophenyl)-9H-carbazole (˜40%) (14.4 g, ˜42 mmol), palladium(II)acetate (1.4 g, 6.3 mmol), triphenylphosphine (3.9 g, 14.7 mmol),N-benzyl-N,N-diethylethanaminium chloride (9.6 g, 42.0 mmol), andpotassium carbonate (29.0 g, 210 mmol) were mixed with 300 mL DMA andthe mixture was degassed before being heated to reflux for 4 hours.After cooling to room temperature, the reaction was filtered through aplug of celite and washed with DCM. The crude material was thenchromatographed on silica with 0-1% DCM in heptane and recrystallizedfrom cold heptane to yield 8.5 g (84%) of indolo[3,2,1-jk]carbazole.

Synthesis of 5-nitroindolo[3,2,1-jk]carbazole

9H-carbazole (10.0 g, 59.8 mmol), 2-chloro-1-fluoro-4-nitrobenzene (10.5g, 59.8 mmol) and potassium carbonate (24.8 g, 179 mmol) were added todimethylacetamide (100 mL) and the mixture heated to 160° C. (bathtemp.) for 16 hours. The reaction was cooled to room temperature andpalladium(II) acetate (0.67 g, 3.0 mmol) and PCy₃-HBF₄ (2.2 g, 6.0 mmol)were added. The reaction mixture was reheated to reflux for 16 hours.The reaction was cooled to room temperature and DCM and 10% LiCl (aq.)were added. After separation, the aqueous was washed twice more with DCMand combined with organics twice with 10% LiCl (aq.), dried over sodiumsulfate and rotovapped (with rotary evaporator) to give 31.1 g of a darksolid. The solid was lixiviated with DCM and filtered to give 7.4 g ofan orange solid (pure product by GC/MS and TLC). The filtrate wasstripped to give 14 g of a dark solid that was chromatographed on silicawith DCM to give 5.6 g of a yellow-orange solid. This solid waslixiviated with heptane and MeOH to give 5.1 g of an orange solid. Thesolids were combined to give 13.5 g (79%) of5-nitroindolo[3,2,1-jk]carbazole.

Synthesis of 6-chloroindolo[3,2,1-jk]carbazole

9-(2-bromo-5-chlorophenyl)-9H-carbazole (9.5 g, 26.6 mmol),palladium(II) acetate (0.90 g, 4.0 mmol), triphenylphosphine (2.4 g, 9.3mmol), N-benzyl-N,N-diethylethanaminium chloride (6.1 g, 26.6 mmol), andpotassium acetate (7.8 g, 80 mmol) were mixed with DMAc (200 mL) and themixture was degassed before being heated to reflux for 4 hours. Aftercooling, the reaction mixture was passed through celite and washed withEtOAc and DCM. After removing the solvents under reduced pressure, 11.1g of a dark yellow solid was obtained. This material was chromatographedon silica gel with 99/1 heptane/DCM to 90/10 heptane/DCM to give 6.7 gof a white solid. This material was recrystallized from DCM/heptane togive 4.4 g (71%) of 6-chloroindolo[3,2,1-jk]carbazole as white needles.

Synthesis of bromoindolo[3,2,1-jk]carbazole

To 9.0 g of indolo[3,2,1-jk]carbazole (37.3 mmol) in 100 mL of DMF at 0°C., NBS (6.6 g, 37.3 mmol) in 50 mL DMF was added dropwise. The reactionwas allowed to warm to room temperature over 16 hours and 100 mL ofsodium metabisulfite solution was added to the reaction. After stirringfor 20 min., the solid was filtered and washed with water and ethanol.The filtrate was extracted 3×100 mL with ethyl acetate and dried oversodium sulfate. After removal of the solvent, the residue was combinedwith the filtered solid and chromatographed on silica gel with 0-3% DCMin heptane to yield 10 g (84%) of a mixture of 60%2-bromoindolo[3,2,1-jk]carbazole and 40%5-bromoindolo[3,2,1-jk]carbazole. The mixture was carried to the nextstep without further purification.

Synthesis of(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)indolo[3,2,1-jk]carbazole:

A mixture of 60% 2-bromoindolo[3,2,1-jk]carbazole and 40%5-bromoindolo[3,2,1-jk]carbazole (10 g, 21.9 mmol),4,4,4′,4′,5,5,5′,5′-octamethyl-2,2′-bi(1,3,2-dioxaborolane) (16.7 g,65.6 mmol), Pd₂(dba)₃ (0.60 g, 0.66 mmol), dppf (0.73 g, 1.3 mmol) andpotassium acetate (6.4 g, 65.6 mmol) in 200 mL dioxane was bubbled withnitrogen for 20 min. and the reaction was allowed to reflux for 16hours. After cooling to room temperature, the reaction was filteredthrough a plug of celite and washed with DCM. The solvent evaporated andexcess (Bpin)₂ was removed by Kugelrohr distillation. The residue waschromatographed on silica with 20-50% DCM in heptane. The product wasrecrystallized from heptane to yield 4.3 g of2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)indolo[3,2,1-jk]carbazole(54%; 31% over 2 steps).5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)indolo[3,2,1-jk]carbazoleeluted after the desired product.

Synthesis of indolo[3,2,1-jk]carbazol-2-ol

Hydrogen peroxide (4.6 mL, 44.9 mmol) was added to2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)indolo[3,2,1-jk]carbazole(3.3 g, 9.0 mmol) in 20 mL of ethanol and the reaction was allowed tostir at room temperature for 16 hours. Hydrogen peroxide (4.6 mL, 44.9mmol) was added once more and the reaction was stirred for 16 hours,filtered and washed with ethanol to yield 1.5 g (65%) ofindolo[3,2,1-jk]carbazol-2-ol as a white solid. The product wasconfirmed by NMR and GC/MS.

Synthesis of indolo[3,2,1-jk]carbazol-2-yl trifluoromethanesulfonate

To indolo[3,2,1-jk]carbazol-2-ol (1.5 g, 5.8 mmol) and pyridine (0.94mL, 11.67 mmol) in 30 mL of DCM at 0° C., trifluoromethanesulfonicanhydride (1.97 mL, 11.66 mmol) was added dropwise. After completion ofthe addition, the reaction was allowed to warm up to room temperaturefor 16 hours and quenched with 50 mL of aqueous potassium carbonatesolution. The aqueous was extracted 3×50 mL with DCM and combinedorganics washed with sodium carbonate and dried over sodium sulfate.After evaporation, the crude product was passed through a plug of silicagel, eluting with DCM. Evaporation of the eluent gave 2.1 g (90%) ofindolo[3,2,1-jk]carbazol-2-yl trifluoromethanesulfonate as a whitesolid. The product was confirmed by NMR.

Synthesis of indolo[3,2,1-jk]carbazol-5-amine

5-nitroindolo[3,2,1-jk]carbazole (12.4 g, 43.3 mmol) was added to aceticacid (100 mL) and 2-propanol (100 mL). Ammonium chloride (0.46 g, 8.7mmol) was dissolved in water (10 mL) and added to the reaction mixture.Iron (9.7 g, 173 mmol) was added slowly in 4×2 g portions and thenheated slowly to 90° C. for 6 hours. The reaction mixture was thencooled to room temperature and filtered through a celite/silica plug andwashed with toluene and DCM. After evaporation of the solvent, the crudematerial was adsorbed on celite and chromaotgraphed on silica with DCMto 9/1 DCM/EtOAc. The resulting product was lixiviated with MeOH to give6.7 g (60%) of indolo[3,2,1-jk]carbazol-5-amine as an orange solid.

Synthesis of 5-iodoindolo[3,2,1-jk]carbazole

In a 1000 mL 2-neck flask with mechanical stirring,indolo[3,2,1-jk]carbazol-5-amine (6.7 g, 26.1 mmol) andp-toluenesulfonic acid monohydrate (24.9 g, 131 mmol) were added tot-BuOH (200 mL) and water (30 mL) and cooled to 10° C. Sodium nitrite(5.4 g, 78 mmol) and potassium iodide (17.4 g, 105 mmol) were dissolvedin water (50 mL) and added dropwise to the reaction mixture, causingimmediate darkening and thickening of the reaction mixture, which waswarmed to room temperature and stirred for 16 hours. Water and MeOH wereadded followed by solid sodium bicarbonate (10.98 g, 131 mmol) and thena saturated bicarbonate solution until the pH was 10-11. Solid sodiumthiosulfate (12.40 g, 78 mmol) was added and the color lightenedconsiderably. The solid was filtered and washed with water and a littleMeOH to give a dark orange solid. The filtrate was washed 3× with DCMand the combined organics with water and brine. This was combined withthe solid above and the solvent removed. The crude product waschromatographed on silica gel with 5-7% DCM in heptane and crystalizedfrom DCM to yield 3.7 g (39%) of 5-iodoindolo[3,2,1-jk]carbazole.

Synthesis of Compound 2

Indolo[3,2,1-jk]carbazol-2-yl trifluoromethanesulfonate (2.0 g, 5.1mmol), 9-phenyl-9H,9′H-3,3′-bicarbazole (2.3 g, 5.6 mmol), Pd₂(dba)₃(0.094 g, 0.10 mmol) anddicyclohexyl(2′,6′-dimethoxy-[1,1′-biphenyl]-2-yl)phosphine (0.17 g,0.41 mmol) were added to m-xylene (50 mL). Sodium tert-butoxide (0.99 g,10.3 mmol) was then added and the mixture was thoroughly degassed beforebeing heated to reflux for 16 hours. After cooling to room temperature,the reaction filtered, washing with toluene. The filtrate was reducedand chromatographed on silica gel with 10-20% DCM in heptane and furtherrecrystallized from heptane to give 0.65 g (20%) of Compound 2 as awhite solid.

Synthesis of Compound 14

9-phenyl-9H,9′H-3,3′-bicarbazole (3.1 g, 7.6 mmol),5-iodoindolo[3,2,1-jk]carbazole (2.8 g, 7.6 mmol), Pd₂(dba)₃ (0.14 g,0.15 mmol), dicyclohexyl(2′,6′-dimethoxy-[1,1′-biphenyl]-2-yl)phosphine(0.25 g, 0.61 mmol) and sodium tert-butoxide (2.2 g, 22.9 mmol) wereadded to m-xylene (75 mL) and the mixture thoroughly degassed beforebeing heated to reflux for 16 hours. The crude reaction mixture wasfiltered through celite and washed with DCM. The filtrate was rotovappedto give 9.0 g of a dark solid. The crude material was chromatorgraphedon silica gel with 8/2 heptane/DCM to 1/1 heptane/DCM. The productfractions were recrystallized form DCM/MeOH to yield 3.8 g (77%) ofCompound 14 as a white solid. The product was confirmed by NMR andLC/MS.

Synthesis of Compound 13

9H-3,9′-bicarbazole (4.2 g, 12.7 mmol), 5-iodoindolo[3,2,1-jk]carbazole(3.9 g, 10.6 mmol), Pd₂(dba)₃ (0.20 g, 0.21 mmol),dicyclohexyl(2′,6′-dimethoxy-[1,1′-biphenyl]-2-yl)phosphine (0.35 g,0.85 mmol) and sodium tert-butoxide (3.1 g, 31.9 mmol) were added tom-xylene (100 mL) and the mixture thoroughly degassed before beingheated to reflux for 16 hours. The crude reaction mixture was cooled andfiltered through celite and washed with DCM and hot toluene. Thefiltrate was reduced and the crude material was chromatographed onsilica gel with 9/1 heptane/DCM to 7/3 heptane/DCM to give 5.5 g (91%)of a Compound 13 as white solid.

Synthesis of Compound 26

9-phenyl-9H,9′H-3,3′-bicarbazole (5.3 g, 13.1 mmol),6-chloroindolo[3,2,1-jk]carbazole (3.0 g, 10.9 mmol), Pd₂(dba)₃ (0.20 g,0.22 mmol), dicyclohexyl(2′,6′-dimethoxy-[1,1′-biphenyl]-2-yl)phosphine(0.36 g, 0.87 mmol) and sodium tert-butoxide (3.1 g, 32.6 mmol) wereadded to m-xylene (80 mL) and the mixture thoroughly degassed beforebeing heated to reflux for 16 hours. After cooling the reaction mixturewas filtered and washed with DCM and EtOAc. The filtered solid wasboiled in hot toluene and filtered through a plug of silica while stillwarm and eluted with more hot toluene. The filtrate was reduced to give7.4 g of an off-white solid, which was recrystallized from toluene togive 5.7 g of Compound 26 as a bright white solid. The product wasconfirmed by NMR and LC/MS.

EXPERIMENTAL

All OLED devices were fabricated by high vacuum (˜10⁻⁷ Torr) thermalevaporation. The anode electrode was 120 nm of indium tin oxide (ITO).The cathode electrode consisted of 1 nm of LiF followed by 100 nm of Al.All devices were encapsulated with a glass lid sealed with an epoxyresin in a nitrogen glove box (<1 ppm of H₂O and O₂) immediately afterfabrication, and a moisture getter was incorporated inside the package.

Device 1a.

This device has organic stacks consisting of, sequentially, from the ITOsurface, 10 nm of LG101 (from LG Chem) as the hole injection layer(HIL), 40 nm of Compound HTM as the hole-transport layer (HTL), 5 nm ofCompound 26 as an electron-blocking layer (EBL), 30 nm of Compound HAdoped with 12% of Compound GD as the emissive layer (EML). On top of theEML, 5 nm of Compound HA was deposited as the hole blocking layer (HBL),followed by 45 nm of tris(8-hydroxyquinolinato)aluminum (Alq₃) as theelectron-transport layer (ETL). The structures of the compounds used areshown below.

Device 1b.

Device 1b has the same structure as that of Device 1a except thatCompound 14 was used as the EBL.

Device 1c.

Device 1c has the same structure as that of Device 1a except thatCompound HB was used as the EBL.

Device 1d.

Device 1d has the same structure as that of Device 1a except thatCompound HD was used as the EBL.

The results of Devices 1a-1d are shown in Table 1 below:

TABLE 1 Luminous Efficacy Device EBL at 1000 nits (cd/A) Device 1aCompound 26 70.1 (inventive) Device 1b Compound 14 71.9 (inventive)Device 1c Compound HB 54.8 (comparative) Device 1d Compound HD 67.1(comparative)

As can be seen from Table 1, the luminous efficacy of the inventivecompounds are high at 70.1 cd/A for Compound 26 and 71.9 cd/A forCompound 14. This is especially striking when compared to thecomparative devices using Compound HB (54.8 cd/A) and Compound HD (67.1cd/A). The data shows that the electronic structure of the inventivecompounds is better disposed to serve as an electron blocking layerrelative to the comparative examples. However, this not obvious fromlooking at the chemical structures of the compounds.

Device 2a.

A second set of device has organic stacks consisting of, sequentially,from the ITO surface, 10 nm of LG101 (from LG Chem) as the holeinjection layer (HIL), 40 nm of Compound HTM as the hole-transport layer(HTL), and 30 nm of emissive layer (EML). On top of the EML, 5 nm ofCompound HC was deposited as the hole blocking layer (HBL), followed by45 nm of tris(8-hydroxyquinolinato)aluminum (Alq₃) as theelectron-transport layer (ETL). The EML consists of three components: 70wt % of Compound 26 is used as the host, with 20 wt % of Compound HC asco-host, and 10 wt % of Compound GD as emissive dopant.

Device 2b.

Device 2b has the same structure as that of Device 2a except thatCompound 13 was used as the host instead of Compound 26.

Device 2c.

Device 2c has the same structure as that of Device 2a except thatCompound HD was used as the host instead of Compound 26.

The results for Devices 2a, 2b, and 2c are shown in Table 2 below:

TABLE 2 EML Compounds Luminous Efficacy Device Host Co-host Dopant at1000 nits (cd/A) Device 2a Compound 26 HC GD 65.4 (inventive) Device 2bCompound 13 HC GD 74.6 (inventive) Device 2c Compound HD HC GD 61.8(comparative)

As can be seen from Table 2, the luminous efficacy of the inventivecompounds, when used as hosts along with co-host HC are high at 65.4cd/A for Compound 26 and 74.6 cd/A for Compound 13. This is especiallystriking when compared to the comparative device using Compound HD (61.8cd/A) as a host. Again, the inventive compounds described herein show aremarkable ability to act as hole-transporting hosts when used incombination with an electron-transporting host (HC), which is notapparent from the chemical structure alone when compared to thecomparative examples.

We claim:
 1. A compound having a structure according to a formulaG¹-G²-G³-G⁴-G⁵, Formula I; wherein G¹ has the structure:

wherein R¹ and R³ each independently represent mono, di, tri, or tetrasubstitutions, or no substitution, wherein R² represents mono, di, ortri substitutions, or no substitution, wherein R¹, R², and R³ are eachindependently selected from the group consisting of hydrogen, deuterium,halogen, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy,amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl,heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile,sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof;wherein G² and G⁴ are each independently selected from the groupconsisting of a direct bond, an aryl group having from 6-30 carbonatoms, a heteroaryl group having from 3-30 carbon atoms, andcombinations thereof, wherein the aryl group and the heteroaryl groupare optionally further substituted with one or more groups selected fromhydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, arylalkyl,alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl,alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester,nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, andcombinations thereof; and wherein G³ and G⁵ are each independently acarbazole or a carbazole that is substituted with one or more groupsselected from hydrogen, deuterium, halogen, alkyl, cycloalkyl,heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl,cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl,carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl,sulfonyl, phosphino, and combinations thereof.
 2. The compound of claim1, wherein G¹ connects to G² at the ring having R² substituent.
 3. Thecompound of claim 1, wherein G¹ connects to G² at the ring having R³substituent.
 4. The compound of claim 1, wherein G² and G⁴ are each adirect bond.
 5. The compound of claim 1, wherein the compound has astructure:

wherein R⁴ represents mono, di, tri, or tetra substitutions, or nosubstitution; wherein R⁵ represents mono, di, or tri substitutions, orno substitution; wherein R⁴ and R⁵ are each independently selected fromthe group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl,heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl,cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl,carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl,sulfonyl, phosphino, and combinations thereof.
 6. The compound of claim1, wherein the compound has a structure:

wherein R⁶, and R⁷ each independently represents mono, di, tri, or tetrasubstitutions, or no substitution; wherein R⁶, and R⁷ are eachindependently selected from the group consisting of hydrogen, deuterium,halogen, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy,amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl,heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile,sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof. 7.The compound of claim 1, wherein the compound has a structure selectedfrom the group consisting of:

wherein R⁴ represents mono, di, or tri substitutions, or nosubstitution; wherein R⁵ represents mono, di, tri, or tetrasubstitutions, or no substitution; wherein R⁴, R⁵, and R⁸ are eachindependently selected from the group consisting of hydrogen, deuterium,halogen, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy,amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl,heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile,sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof. 8.The compound of claim 1, wherein the compound has a structure:

wherein R⁶, and R⁷ each independently represents mono, di, tri, or tetrasubstitutions, or no substitution; wherein R⁶, R⁷, and R⁹ are eachindependently selected from the group consisting of hydrogen, deuterium,halogen, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy,amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl,heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile,sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof. 9.The compound of claim 1, wherein the compound has a structure selectedfrom the group consisting of:

wherein R⁴, R⁶, and R⁷ each independently represents mono, di, tri, ortetra substitutions, or no substitution; wherein R⁵ represents mono, di,or tri, substitutions, or no substitution; wherein R⁴, R⁵, R⁶, R⁷, R⁸,and R⁹ are each independently selected from the group consisting ofhydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, arylalkyl,alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl,alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester,nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, andcombinations thereof.
 10. The compound of claim 1, wherein G¹ isselected from the group consisting of:


11. The compound of claim 1, wherein the compound is selected from thegroup consisting of:


12. A device comprising one or more organic light emitting devices, atleast one of the organic light emitting devices comprising: an anode; acathode; and an organic layer, disposed between the anode and thecathode, comprising a compound having the formula G¹-G²-G³-G⁴-G⁵,Formula I; wherein G¹ has the structure:

wherein R¹ and R³ each independently represent mono, di, tri, or tetrasubstitution, or no substitution; wherein R² represents mono, di, or trisubstitution, or no substitution; wherein R¹, R², and R³ are eachindependently selected from the group consisting of hydrogen, deuterium,halogen, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy,amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl,heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile,sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof;wherein G² and G⁴ are each independently selected from the groupconsisting of a direct bond, an aryl group having from 6-30 carbonatoms, a heteroaryl group having from 3-30 carbon atoms, andcombinations thereof; wherein the aryl group and the heteroaryl groupare optionally further substituted with one or more groups selected fromhydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, arylalkyl,alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl,alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester,nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, andcombinations thereof; and wherein G³ and G⁵ are each independently acarbazole or a carbazole that is substituted with one or more groupsselected from hydrogen, deuterium, halogen, alkyl, cycloalkyl,heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl,cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl,carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl,sulfonyl, phosphino, and combinations thereof.
 13. The device of claim12, wherein the organic layer is an emissive layer and the compound is ahost.
 14. The device of claim 12, wherein the organic layer furthercomprises a phosphorescent emissive dopant.
 15. The device of claim 14,wherein the phosphorescent emissive dopant is a transition metal complexhaving at least one ligand or part of the ligand, if the ligand is morethan bidentate, selected from the group consisting of:

wherein R_(a), R_(b), R_(c), and R_(d) may represent mono, di, tri, ortetra substitution, or no substitution; wherein R_(a), R_(b), R_(c), andR_(d) are independently selected from the group consisting of hydrogen,deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy,aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl,aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile,isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinationsthereof; and wherein two adjacent substituents of R_(a), R_(b), R_(c),and R_(d) are optionally joined to form a fused ring or form amultidentate ligand.
 16. The device of claim 15, wherein thephosphorescent emissive dopant is selected from the group consisting of:


17. The device of claim 12, wherein the organic layer is an electronblocking layer and the compound having Formula I is an electron blockingmaterial in the organic layer.
 18. The device of claim 12, wherein theorganic layer is an electron transporting layer and the compound havingFormula I is an electron transporting material in the organic layer. 19.The device of claim 12, wherein the device is selected from the groupconsisting of a consumer product, an electronic component module, anorganic light-emitting device, and a lighting panel.
 20. A formulationcomprising the compound in claim 1.